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Journal of Cleaner Production 18 (2010) 395–401

Journal of Cleaner Production 18 (2010) 395–401 Contents lists available at ScienceDirect Journal of Cleaner

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.else vier.com/locate/jclepro Formic and acetic acid as agents for a cleaner fractionation

Formic and acetic acid as agents for a cleaner fractionation of Miscanthus x giganteus

Juan Jose´ Villaverde, Pablo Ligero, Alberto de Vega *

Department of Physical Chemistry and Chemical Engineering, University of A Corun˜a, A Corun˜a 15071, Spain

article info

Article history:

Received 19 May 2009 Received in revised form 21 October 2009 Accepted 29 October 2009 Available online 6 November 2009

Keywords:

M. x giganteus Delignification Organosolv fractionation Acetic acid Formic acid Kinetics

abstract

Miscanthus. x giganteus bark was subjected to acetic and formic acid fractionation. The kinetics of the process were explained by a model of two parallel first-order reactions, for pulp yield and delignification, and by Saeman’s kinetics based models, for total polysaccharides and viscosity of pulps. The influence of hydrochloric acid concentration on both organosolv processes was studied at two levels: 0.10 and 0.15% by weight. The models provided a good fit of the experimental data and helped to predict the best set of independent variables to obtain a good fractionation. Both systems achieved similar delignification levels and pulp characteristics, although the evolution in formic acid was faster than in acetic acid, mainly due to the great extent of reactions in the warming up period that accounted for about a third part of the initial dry weight of the raw material. 2009 Elsevier Ltd. All rights reserved.

1. Introduction

The fast human development since half of the XVIII century is based on the exploitation of fossil sources. However, in the 1960s the first clear evidence of environmental impacts of the industrial development, and later in the early 1970s, with the first oil crisis, demonstrated the risk of the dependence on fossil sources. The development and decline of civilizations or societies based on the overexploitation and exhaustion of natural sources, accompanied by serious environmental damage is not a new phenomenon [1] . To overcome such risk, society must start to prepare the transition from a development model based on non-renewable, to a renew- able resources based model, in order to no longer depend on fossil sources. Vegetal biomass looks the most logical solution for the sustainable production of energy and chemicals. Among these renewable biomass sources, different non-woody materials, such as annual and perennial grasses, should become the object of impor- tant research work for industrialised countries if they want to fulfil their demands. Nowadays the kraft process still continues to be the predomi- nant method to produce cellulose pulps from lignocellulosic materials. But the Kraft process is accompanied by significant

* Corresponding author. Fax: þ 34 981 167065. E-mail address: devega@udc.es (A. de Vega).

0959-6526/$ – see front matter 2009 Elsevier Ltd. All rights reserved.

doi:10.1016/j.jclepro.2009.10.024

environmental problems derived from cooking with sulphur compounds that generate malodour substances like hydrogen sulphide, methyl mercaptan and dimethyl sulphide, and from, in some cases the bleaching of pulps with chloride compounds [2] which have not yet been completely solved [3] . Furthermore, the growing world demand of pulp for paper has unquestionable impacts on forests. Nevertheless an alternative approach to exploit lignocellulosic materials is available. With regard to cooking, it is obvious that the best way to avoid the problems associated with the use of sulphur compounds is not to use them. This idea has led the design and improvement of organosolv processes. In short, in an organosolv process, the removal of lignin from the solid matrix, is achieved replacing sulphur compounds by organic solvents. These organic compounds (with or without the aid of small amounts of mineral acid) produce the delignification of the raw material in a more gentle and effective way than the kraft process does. This milder way to operate means that the natural polymers present in plant material are separated in a less degraded way, thus opening up possibilities for its use with higher added value, while lignin solubilised in kraft process is on-site burned to produce energy, adding more environmental impacts [4] . In other words, organo- solv processes can be designed as fractionation methods rather than pulping methods [5] . That is, they could be operated to virtually achieve a complete exploitation (fractionation) of raw materials, yielding the main components of vegetal tissues (cellu- lose, hemicelluloses and lignin) in a less degraded form [6] . This

396

J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395–401

characteristic can open promising perspectives for the integrated exploitation of the biomass, within the concept of the biorefinery [7] , similar to that of an oil refinery, whose main goal is to take advantage of the compositional diversity of biomass to produce high-value low-volume and low-value high-volume products and energy using different concurrent methods, while minimizing waste streams [7] . The genus Miscanthus comprises a number of tall perennial rhizomatous grasses, belonging to Poaceae family, with C 4 photo- synthesis, native of tropics and subtropics, with an excellent productivity, fast grown and low sensitive to illness [8] . Among these grasses, Miscanthus x giganteus Greef & Deuter ex Hodkinson

& Renvoize [9] , a sterile hybrid horticultural genotype, has attracted

the interest of the EU authorities as a biomass source. In 1993,

a project was set up under the European AIR program to know the

potential and limitations of M. x giganteus in Europe, and organo- solv fractionation were carried out within the biorefinery perspective [10,11] . First designed for energy applications [12] , immediately it began to be investigated for its possible utilization by chemical methods. Acetic and formic acid, using hydrochloric acid as catalyst (henceforth Acetosolv and Formosolv), have proved to be good lignin solvents for Miscanthus , among others [13] , yielding satis- factory levels of delignification and physical properties [10,11] . This work was carried out in order to establish the kinetic interrela- tionships between the operational variables (time and catalyst concentration) and yield, Klason lignin, intrinsic viscosity, and carbohydrate content of pulps in treatments of M. x giganteus with acetic and formic acid fractionation systems catalyzed with hydrochloric acid. From the experimental data, a quantitative interpretation of the experimental results, by kinetic models, was developed. This work is complementary to other organosolv fractionation studies with M. x giganteus by short chain carboxylic acids [10,11] , and will assess the optimal fractionation conditions to use in future studies of bleaching and exploitation of recovered hemicelluloses and lignin.

2. Material and methods

2.1. Raw material

2.3. Analytical methods

Pulp yield (PY) was determined gravimetrically after drying to constant weight. Lignin in raw material and pulps (residual Klason lignin in pulp, RKL) was determined by weighing the residue obtained following two-stage Klason digestion with 72% H 2 SO 4 for 2 h at 15 C followed by 3% H 2 SO 4 for 1 h at 120 C (TAPPI T222 om-88). Other standard TAPPI procedures were used to determine the kappa number (KN) (TAPPI T236), intrinsic viscosity (VIS) of pulps (TAPPI T230), ash (TAPPI T 211 om-02), and pentosans (TAPPI T223 om-84). Total polysaccharide content of pulps (TP) was quantified by spectrophotometric determination of reducing sugars in the Klason hydrolysate by the Somogyi–Nelson method. Holocellulose was determined by the chlorite method according to Browning [14] .

2.4. Fitting of data

Non-linear regressions between experimental data and proposed models were performed using commercial software (Statgraphics 5.0 from Manugistics).

3. Results and discussion

The chemical composition of depithed M. x giganteus stem, on a dry weight basis, was determined analytically as 26.1% Klason lignin (3 replications, standard deviation 0.42), 73.3% holocellulose (2 replications, standard deviation 2.30), 18.8% pentosans (2 repli- cations, standard deviation 0.47), and 0.4% ash (3 replications, standard deviation 0.12). Previous works [10,11] and preliminary experiments showed that extensive delignification can be achieved under organic acid concentrations of 90 weight% for Acetosolv and Formosolv systems, using a liquor/wood ratio ¼ 12 w/w, and small proportions of hydrochloric acid as catalyst. In order to further assess the best HCl concentration to achieve the more suitable fractionation of the raw material, a kinetic monitoring was performed in which two different concentration of mineral acid were used (0.10% and 0.15% by weight) in the range 0–180 min.

M. x giganteus was collected from an experimental plantation established near Santiago de Compostela (Galicia, Spain) as a result of the EU AIR Miscanthus Productivity Network project [8] . Stems were harvested, and after air drying period, manually stripped of leaves and core. Bark was milled to pass a 1 cm screen, let to attain its equilibrium moisture and finally stored in hermetic plastic bags.

2.2. Kinetic studies

Fractionation kinetic studies were performed using mixtures of ground M. x giganteus , water and acetic or formic acid, heated to boiling point in 250 cm 3 Pyrex flasks. In this moment hydrochloric acid was added, taking this as time zero. The selected concentra- tions of hydrochloric acid were 0.10 and 0.15%, according to the best results found in previous work [10,11] . The mixtures were refluxed with stirring at atmospheric pressure along a desired time. Reac- tions were stopped by removing the flasks from the heating plates and by fast filtration through medium-pore Gooch crucibles to separate pulp and black liquors. Then pulps were treated four times with 85% acetic (in acetic acid system) and 80% formic acid (in formic acid system) in w/v proportions of 0.4, 0.4, 0.2 and 0.2 in relation to the initial dry weight of M. x giganteus . Finally, pulps were washed with distilled water until the washings were neutral.

3.1. Pulp yield and delignification

Kinetics profiles of PY and RKL are very similar ( Fig. 1 ): a high decrease is observed in the first minutes, followed by a slow phase where values tend to an asymptotic limit. To simulate this behav- iour, researchers usually have utilised a phenomenological kinetic model based on the supposition of two simultaneous pseudo-first order reactions taking place [15,16] . This approach involves the existence of two fractions of materials/lignin with different susceptibilities towards solubilisation/delignification. One fraction shows high ability to solubilise/delignify, reacting rapidly thus becoming predominant at short times, while the second is difficult to solubilise/delignify and proceeds slowly during more prolonged times. Such stages are usually referred in bibliography as bulk and residual phases, respectively. As a strict kinetic model is not possible to build, due to the substrate heterogeneity and complexity, the following were assumed.

The model will be built as for a homogeneous system. Due to the impossibility to know molecular weights of involved species, the formulation of the model in molar units was let apart and replaced for dry weight percentages.

J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395–401

397

a 95 90 A cet osol v, 0 . 10 % H Cl 85 Acetosolv
a
95
90
A
cet osol v, 0 . 10 % H Cl
85
Acetosolv Ace toso lv, 0 0. 15% 15% HCl HCl
80
F
o r mos ol v, 0. 1 0% H C l
75
Fo Formosolv, rm osol v, 0. 0.1 15% 5% HCl HCl
70
65
60
55
50
45
Pul p yield (% d.b.)

00

2200

4400

6600

8800

110000

Time (min.)

112200

114400

116600

118800

220000

25 b Acetosol v, 0 . 10% H Cl AAcceettoossoollvv, 00.1155%% HHCCll 20 0 F
25
b
Acetosol v, 0 . 10% H Cl
AAcceettoossoollvv, 00.1155%% HHCCll
20
0
F or mos o lv, 0. 10% H C l
FFoorrmmoossoollvv,, 00
1155%%
HHCCll
15
5
10
5 5
0
Residual Klason lignin (% d.p.b.)

0

20

40

60

80

100

Time (min.)

120

140

160

180

200

Fig. 1. Experimental data and fitted curves for the pulp yield and Klason lignin remaining in pulp.

As said above it is supposed that both reactions agree with a first-order progress with time. That is they follow pseudo- first order kinetics.

Chemical equations for the formulation for this process are:

where

X f

X s

k f k s
k f
k
s

Solubilised

materials

X f and X s are the percentages, at time t , of solids or lignin that undergo the fast and slow reaction, respectively.

X f0 and X s0 are the percentage, at time zero, of solids or lignin

that undergoes the fast and slow reaction, respectively.

k f and k s are the rate constants of fast and slow reaction, respectively.

t is the reaction time.

The integrated equations for this system are:

X f ¼

X f 0 e k f t

X s ¼ X s 0 e k s t

So, for a given time, PY can be measured as the sum of contri- butions of the fast and slow reacting fractions:

PY ¼ PY f þ PY s ¼ PY f 0 e k f t þ PY s 0 e k s t ¼ ð PY tot 0 PY s 0 Þ e k f t þ PY S 0 e k s t

In a similar way, for RKL:

RKL ¼ RKL f þ RKL s ¼ RKL f 0 e k f t þ RKL S 0 e k s t ¼ ð RKL tot 0 RKL s 0 Þ e k f t þ RKL S 0 e k s t

Table 1 lists the obtained regression parameters for k f , k s , X tot0 and X s0 when the data of Table 2 were fitted to previous equations, as well the R 2 statistical parameter measuring the correlation of equations. Fitting of data resulted in a good correlation between time and both PY and RKL ( Fig. 1 ). From observation of Fig. 1 and values of PY tot0 ( Table 1 ) it can be inferred that an extensive solubilisation occurred during heating period, which accounted for about 15% and 33% for acetic and formic acid, respectively. In a similar way, delignification in the heating period was more important for formic

acid ( Fig. 1 and Table 1 ). As expected, parameters PY tot0 and RKL tot0 diminished as hydrochloric acid concentration rise, reflecting the influence of mineral acid. Fig. 1 also reveals a higher solubilising ability of formic acid: yields around 47% were obtained for long lasting reactions, instead around 55% for acetic acid.

A similar trend is observed in the behaviour of RKL: a fast

reaction in the first minutes, followed by a residual slow process. Nevertheless significant differences were observed between the

two processes. The end of the fast reaction depends on the organic acid and on the studied variable ( Fig. 1 and Table 1 ): for PY, the fast reaction appears to be stopped almost at the same time (aprox. 25 min) in the two systems, followed for a slow solubilisation that

seemed not to be dependent on HCl concentration (similar k f for both systems). For RKL, the Formosolv system follows a similar trend: a comparatively very fast reaction until about 25 min, and

a residual stage from this time on, whereas Acetosolv system shows

a smoother fast delignification as it is more prolonged in time, until approx. 50–60 min. Furthermore, the k s showed a significant difference; their values for Acetosolv system are roughly 10 times higher, which means that, while Formosolv delignification was

Table 1 Values of the kinetic parameters for the solubilisation and delignification processes obtained by non-linear regression.

 

Regression parameters

Acetic acid

Formic acid

0.10% HCl

0.15% HCl

0.10% HCl

0.15% HCl

RKL

PY

RKL

PY

RKL

PY

RKL

PY

X tot0 (% d.m.) X f0 (% d.m.) X S0 (% d.m.) k f (min 1 ) k s (min 1 ) R 2

23.30

82.37

23.78

88.32

15.83

71.25

11.78

62.02

17.21

20.24

17.83

26.81

11.69

15.84

6.87

6.63

6.09

62.14

5.95

61.51

4.14

55.41

4.91

55.39

0.0560

0.1056

0.0951

0.0891

0.1745

0.3560

0.1535

0.1543

0.0051

0.00077

0.0071

0.00069

0.00016

0.00085

0.0026

0.0010

0.9973

0.9672

0.9916

0.9826

0.9668

0.9673

0.9603

0.9088

Total polysaccharides in pulp (%d.b.)

398

J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395–401

Table 2 PY, RKL, TP and VIS of pulps obtained in each treatment.

 

Time (min) Acetic acid

 

Formic acid

 
 

0.1% by weight

 

0.15% by weight

 

0.1% by weight

 

0.15% by weight

 

PY (%)

RKL (%) TP (%)

VIS (mL/g)

PY (%)

RKL (%) TP (%)

VIS (mL/g)

PY (%) RKL (%)

TP (%)

VIS (mL/g)

PY (%) RKL (%)

TP (%) VIS (mL/g)

0

83.2

23.5

70.6

120

88.4

23.9

73.6

213

71.3

16.1

77.9

350

62.0

11.8

78.9

573

5

72.1

18.6

76.6

237

78.6

16.6

77.6

308

57.3

7.9

86.2

1085

58.5

7.9

85.2

1053

10

67.9

15.4

80.5

301

72.2

12.3

81.0

399

56.6

7.0

87.8

1130

55.6

6.6

86.7

1221

15

67.6

13.6

81.1

420

66.8

10.1

83.3

468

56.8

5.4

88.6

1142

54.9

5.2

88.2

1225

20

63.4

10.9

85.7

386

64.5

7.5

88.8

612

53.4

4.9

89.5

1138

54.5

4.9

89.7

1168

25

63.3

9.9

90.1

429

64.1

6.4

90.7

685

53.0

4.7

90.6

1085

56.1

4.2

90.1

1107

30

62.3

8.2

91.0

526

63.3

6.1

90.8

716

53.4

4.5

91.6

1131

54.7

5.5

90.5

1069

40

60.1

6.9

92.2

666

61.9

5.8

91.0

913

52.9

3.8

92.2

1098

53.5

4.8

91.0

1094

50

59.9

5.6

93.6

752

60.2

4.1

92.3

942

54.0

4.2

92.5

1045

53.3

4.4

91.3

879

60

59.1

5.4

92.3

809

56.9

3.5

90.1

1017

53.3

3.8

92.8

1084

52.4

4.3

92.1

1005

70

60.5

4.3

93.0

1078

60.2

3.4

91.7

966

52.0

3.6

93.6

1054

49.8

3.5

90.4

973

80

54.9

4.1

93.7

1089

58.6

4.4

91.2

1093

51.9

3.5

92.9

1057

51.9

4.5

90.7

944

90

57.0

3.8

93.5

1066

55.8

2.4

91.0

1057

51.0

3.6

92.0

993

48.0

3.2

89.6

999

100

58.7

4.4

93.4

929

57.9

2.2

90.7

1151

51.1

3.7

94.0

948

50.4

3.4

90.9

974

120

56.7

2.9

92.1

1129

55.1

2.6

91.7

1105

48.6

3.7

92.5

886

48.6

3.5

90.4

908

150

55.5

3.0

93.8

1120

54.9

1.8

91.2

1016

50.0

5.0

91.9

851

47.1

3.4

90.6

853

180

54.7

2.4

93.2

1058

56.0

2.6

91.7

969

47.6

4.3

91.4

838

48.7

3.6

90.9

951

virtually stopped at around 40 min, Acetosolv solubilisation of lignin continues in an almost linear process until 180 min. This could make possible an extended delignification that could not be accomplished in the Formosolv system. In fact, the differences of RKL, predicted by the models, between both systems for the most prolonged experiments are lower in the acetic process by 1.4 and 1.6%. Nevertheless, no clear signs of lignin recondensation and/or reprecipitation were observed for the two systems. No important differences in solubilisation were found when comparing the use of one or other HCl concentrations. The same was observed for delignification with formic acid: both fitted curves are almost superimposed. Acetosolv delignification revealed more sensitivity to HCl concentration since k f for 0.15% HCl is roughly twice that k f for 0.10% HCl. In other words, the fitted line for 0.15% HCl is always below the corresponding to 0.10%, what means lower lignin content in pulp is obtained, for the same time treatments, when working with 0.15%.

3.2. Total polysaccharides in pulp

The determination of reducing sugars after quantitative hydro- lysis of pulps was performed for all samples. These data are related with the process of cellulose purification which is concurrent with delignification. Results ( Fig. 2 ) show a very fast enrichment in cellulose in the first minutes, is in accordance with the already mentioned fast delignification phase, followed by an almost hori- zontal profile. This means that purified cellulose in pulp suffered

a moderate subsequent damage by acid hydrolysis. This was also

confirmed by mass balances, since if there was no degradation, the values of (100 RKL) should provide, for each treatment time, the value of TP (given the low proportion of extractives which more- over should be mostly solubilised). Therefore, in order to simulate the kinetic behaviour of total polysaccharides a simple phenomenological model, based on that of Saeman [17] , was used, in which two consecutive set of phenomena were taken into account (assuming that both follow pseudo-first order kinetics): A first group of reactions combining all the reactions that finally result in the solubilisation of lignin, hemicelluloses and other components, thus enriching the content

of polysaccharides in pulp, and a second one accounting for all the degradation paths, mainly hydrolytic, of polysaccharides. Thus, in

a very simplified way, we can write

Polysaccharides in ‘‘unpurified”

Polysaccharides in ‘‘purified”

Pup / TP / HP

k

S

k

H

pulp

pulp

k

S

!

Solubilisation

k

H

! HP

Degradation

The rate equation for the content of polysaccharides in pulp is:

d ð TP Þ

d t

¼ k S ð Pup Þ k H ð TP Þ

and the corresponding integrated expression:

TP ¼ ð TP Þ 0 e k H t þ ð Pup Þ 0

where:

k

S

k S e k S t e k H t

k H

(TP) 0 and (Pup) 0 are constant of the model that can be identi- fied as the fraction of pulp polysaccharides, at time zero, available and unavailable for degradation composition, respectively. k 1 and k 2 are the pseudo-first order rate constants for the solubilisation and degradation reactions, respectively.

100

95

90

85

80

75

70

Acet oso lv, 0 .1 0% HC l Acetosolv,.0 15% HCl F o rm os
Acet oso lv, 0 .1 0% HC l
Acetosolv,.0 15% HCl
F
o rm os ol v, 0 . 1 0 % HC l
FFoorrmmoossoollvv,, 00
1155%%
HCl
0
20
40
60
80
100
120
140
160
180
200

Time (min.)

Fig. 2. Experimental data and fitted curves for the total content of polyscaccharides in pulp.

J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395–401

399

Table 3 Values of the kinetic parameters for total polysaccharides content of pulps obtained by non-linear regression.

 
 

Regression parameters

Acetic acid system

Formic acid system

 

0.10% HCl

0.15% HCl

0.10% HCl

0.15% HCl

Total polysaccharides in pulp (TP)

C 0 (% d.m.) P 0 (% d.m.) k 1 (min 1 ) k 2 (min 1 ) R 2 t max (min) TP max (% d.m.)

70.3

72.5

79.0

79.2

24.5

19.8

14.0

11.8

0.0549

0.0697

0.0893

0.1103

0.00012

0.000086

0.000058

0.000033

0.9777

0.9605

0.9463

0.9679

87

74

61

55

93.7

91.6

92.6

90.8

Intrinsic viscosity (VIS)

VIS 0 (mL/g) B (mL/g) k 1 (min 1 ) k 2 (min 1 ) R 2 t max (min) VIS max (mL/g)

103

192

350

571

1987

1607

828

585

0.0100

0.0160

0.446

0.441

0.00424

0.00445

0.00201

0.00185

0.9620

0.9870

0.9825

0.8045

144

104

11

11

1114

1101

1150

1131

Due to the high empirical grade of the proposed model, the parameters (TP) 0 and (Pup) 0 are difficult to explain on a strict chemical basis, but the fitting of data resulted in a good correlation between time and measured total polysaccharides in pulp ( Fig. 2 and Table 3 ), giving a simpler equation to simulate the behaviour of cellulose during reaction. Fitting parameters are presented in Table 3 . As can be seen from Table 3 decomposition reactions of poly- saccharides are greatly restricted, in the time range studied, according to the very low values of the k 2 constants. Nevertheless, the maximum enrichment in polysaccharides is attained in a rela- tively short time that can be calculated from the kinetic model by derivation and equalling to zero the result. Such process yields the following expression for the time to achieve the maximum poly- saccharides content:

t max ¼ ln a C 0 ab

P 0 k 1

b

where:

a ¼ k 2 ; b ¼ k 2 k 1

k

1

And according to this, maximum predicted values ( Table 3 ) around 92% d.m. could be achieved in relatively short times between 55 and 87 min. Formosolv system evolutes a bit quickly than Acetosolv, probably due to its higher solubilising power in the heating period that contributes to a more important enhancement

8 . 0 A cetosolv, 0.10% H Cl 7 7.5 5 Aceto solv, 0 .15
8
. 0
A cetosolv, 0.10% H Cl
7
7.5
5
Aceto solv, 0 .15 % HC l
Fo r m o s o l v, 0 .1 0 % H C l
7
. 0
Fo Formosolv, rm o s o lv, 0.15% 0. 1 5 % HCl HCl
6
. 5
6
. 0
5
. 5
5
. 0
0
5
10
15
20
25
30
ln (V
Viscosity (m
mL/g)

Residual Klason lignin (% d.p.)

Fig. 3. Dependence of the viscosity with the Klason lignin remaining in pulp.

in polysaccharides content of pulp. Although of lesser importance, hydrolytic effects are observed in Fig. 2 , where the near horizontal phases of the process using 0.15% HCl is below the corresponding to 0.10% for both systems. Also, a small effect is observed in the use of two organic acids, because from the maximum and beyond, acetic acid yielded pulps a bit more purified.

3.3. Viscosity of pulps

Intrinsic viscosity was also determined for all pulps. A fully empirical model was used to obtain regression equations from experimental data. In Fig. 3 , ln (VIS) is represented versus RKL. A clear linear dependence is observed for acetic acid pulps, while Formosolv system seems to follow a similar linear dependence until about 6% RKL, and from here delignification proceeds at the expense of the cellulose viscosity. This suggests an exponential functional dependence of the type VIS ¼ exp (Constant $ RKL) that must be complemented, especially for formic acid ( Fig. 4 ), for hydrolytic decomposition. Moreover, as VIS is closely related to both purity of samples (non-cellulosic compounds present in partially delignified pulps are cross-linked polymers or low molecular mass products that affect not the reproducibility but the reliability of the determination) and polysaccharide chain length (affected by hydrolytic and/or decomposition reactions) a simple model that could reflect this facts was chosen. Again that model was that of Saeman, but in a fully empirical form in order to explain the shape of curves obtained, in which a first stage of purification/

1400 1200 1200 1000 800 Aceto solv, 0.1 5% HCl 600 Acetoso lv, 0.15% HCl
1400
1200
1200
1000
800
Aceto solv, 0.1 5% HCl
600
Acetoso lv, 0.15% HCl
400
F
or m o s o lv, 0 . 1 0 % HC l
200
F
o r m o s o l v, 0 . 1 5 % HC l
0
Vis cosity (mL /g)

0

0

20 20

40 40

60 60

80 80

100 100

120 120

Time (min.)

140 140

160 160

180 180

200 200

Fig. 4. Experimental data and fitted curves for the viscosity of pulps.

400

J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395–401

Table 4 Values of DV predicted from regression equations when VIS and TP are maximum.

 

0.10% HCl

0.15% HCl

Acetic acid system t VIS max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

t VIS max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

144

55.6

2.9

93.2

1114

104

57.3

2.9

91.5

1101

t TP max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

t TP max (min.)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

87

58.1

4.0

93.7

1014

74

58.5

3.5

91.6

1059

Formic acid system t VIS max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

t VIS max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

11

55.2

5.9

87.7

1150

11

56.0

6.0

87.5

1131

t TP max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

t TP max (min)

PY (%)

RKL (%)

TP (%)

VIS (mL/g)

61

52.6

4.1

92.6

1045

55

52.4

4.3

90.8

1047

enrichment on cellulose and a second one representing cellulose degradation were taken into account. So, a similar expression to the Saeman’s model can be assumed:

VIS ¼ VIS 0 e k 2 t þ B

k

1

k 2 e k 2 t e k 1 t

k 1

Here, VIS 0 is the intrinsic viscosity at time zero, B and empirical constant, and k 1 and k 2 the corresponding kinetic constants for the pulp cellulose enrichment and cellulose degradation, respectively. Table 3 shows the calculated fitting parameters and Fig. 4 the experimental points and fitted lines for formic and acetic acid systems. Differences in using one or another acid become very clear. Formosolv pulp viscosity grows very fast in the first minutes, reaching its maximum values (1150 and 1131 mL/g for 0.10% and 0.15% HCl, respectively) at 11 min for both HCl concentrations tested. Furthermore, the predicted profiles for these HCl concen- trations are virtually the same ( Fig. 4 ), meaning that the mineral acid does not have influence on pulp viscosity, even in the decom- position phase that could be expected to be dependent on that concentration. The relative high acidity of formic acid could explain this result: the effect of mineral acid is hidden by the greater concentration of formic acid, which contributes to proton formation in much higher extent than HCl. In the case of acetic acid, the situation differs; the more HCl is added the fast maximum viscosity is achieved (144 min for 0.10% HCl, and 104 min for 0.15% HCl), whereas the predicted viscosity values do not differ significantly (1114 mL/g for 0.10% HCl, and 1101 mL/g for 0.15% HCl) ( Table 4 ). Eventually, a look on the evolution graphs for both systems ( Fig. 5 ) enables to conclude that although the evolution is very different depending on the organic acid, as was mentioned, the best

100 90 90 80 80 70 70 Ace to solv 0. 10 % HC l
100
90
90
80
80
70 70
Ace to solv 0. 10 % HC l
Aceto solv 0 .15 % HC l
Form oso l v 0. 1 0% HC l
60
Fo rm osol v 0 . 1 5 % HC l
50
0
250
500
750
1000
1250
1500
Tota
al polysacc
charides in n pulp (% d
d.p.)

Viscosity (mL/g)

Fig. 5. Selectivity graphs for acetic and formic acid fractionation systems.

obtained pulps are very similar in VIS and TP. Therefore, the more suitable conditions must be chosen depending on the rest of dependent variables. Although the models predict very similar values for VIS and TP, around the maxima calculated ( Table 4 ), small differences were found for PY and RKL, being its values more favourable to Acetosolv system: 3.3% higher in PY, and 1.8% lower in RKL, in average.

4. Conclusions

Acetic and formic acid systems were modelled with the proposed kinetic models, and the used equations provided a satis- factory prediction of the experimental data. M. x giganteus pro- cessing with HCl as catalyst of aqueous mixtures of acetic and formic acid provides an efficient way to separate the main fractions of this grass. Thus, the presented kinetic models in this work provide valuable information necessary to evaluate the feasibility of the studied process. Although Formosolv system, during the warming up period, dissolves a higher amount of lignin from M. x giganteus , achieving earlier a higher content of TP, Acetosolv system, after adding the catalyst, is more efficient than Formosolv system. The small effect observed in Formosolv system from the catalyst addition is presumably due to a higher saturation of solution with soluble lignin and carbohydrates during heating, and to the higher acidity of formic acid in relation to acetic, that hides the effect of hydro- chloric acid. Taking this into account, 0.10% HCl seems the more adequate concentration to use in the formic acid system. In view of the VIS and TP behaviour along the process, in the acetic system, hemicelluloses together with lignin are dissolved during reaction (hence VIS ascent), and only after the more prolonged treatments cellulose is degraded. Formic acid system evolution in the warming up period is very important since significant proportions of lignin are dissolved, whereas in acetic acid system this effect is much lower. This is probably due to the higher acidity constant of formic acid, which is 10 times higher than that of acetic acid. Therefore, in Formosolv system, the necessary time to get a pulp with kappa near 20 to start with a bleaching process is achieved before than with Acetosolv system. Also, for a given HCl concentration, TP curves in the formic acid system always are below to the corresponding to acetic acid system, which means that Formosolv system is less efficient for elimination of lignin than Acetosolv.

Acknowledgments

The authors are grateful to ‘‘Xunta de Galicia’’ for their granting of the research project (PGIDIT04RFO2659912PR: Obtencio´ n de

J.J. Villaverde et al. / Journal of Cleaner Production 18 (2010) 395–401

401

biopolı´ meros de orixe vexetal a partir da biomasa do Miscanthus sinensis , en condicio´ ns de cultivo enerxe´ tico, por procedementos solvolı´ ticos), to Dr. D. Manuel Bao Iglesias, from University of Santiago de Compostela, for the kind supply of M. x giganteus , and to University of A Corun˜ a to grant a predoctoral fellowship to Mr. J. J. Villaverde.

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